WO2007149175A2 - Aqueous compositions useful in filling and conveying of beverage bottles wherein the compositions comprise hardness ions and have improved compatibility with pet - Google Patents
Aqueous compositions useful in filling and conveying of beverage bottles wherein the compositions comprise hardness ions and have improved compatibility with pet Download PDFInfo
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- WO2007149175A2 WO2007149175A2 PCT/US2007/012275 US2007012275W WO2007149175A2 WO 2007149175 A2 WO2007149175 A2 WO 2007149175A2 US 2007012275 W US2007012275 W US 2007012275W WO 2007149175 A2 WO2007149175 A2 WO 2007149175A2
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Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M173/00—Lubricating compositions containing more than 10% water
- C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
- C10M173/025—Lubricating compositions containing more than 10% water not containing mineral or fatty oils for lubricating conveyor belts
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M173/00—Lubricating compositions containing more than 10% water
- C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65G—TRANSPORT OR STORAGE DEVICES, e.g. CONVEYORS FOR LOADING OR TIPPING, SHOP CONVEYOR SYSTEMS OR PNEUMATIC TUBE CONVEYORS
- B65G17/00—Conveyors having an endless traction element, e.g. a chain, transmitting movement to a continuous or substantially-continuous load-carrying surface or to a series of individual load-carriers; Endless-chain conveyors in which the chains form the load-carrying surface
- B65G17/30—Details; Auxiliary devices
- B65G17/32—Individual load-carriers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B67—OPENING, CLOSING OR CLEANING BOTTLES, JARS OR SIMILAR CONTAINERS; LIQUID HANDLING
- B67C—CLEANING, FILLING WITH LIQUIDS OR SEMILIQUIDS, OR EMPTYING, OF BOTTLES, JARS, CANS, CASKS, BARRELS, OR SIMILAR CONTAINERS, NOT OTHERWISE PROVIDED FOR; FUNNELS
- B67C3/00—Bottling liquids or semiliquids; Filling jars or cans with liquids or semiliquids using bottling or like apparatus; Filling casks or barrels with liquids or semiliquids
- B67C3/02—Bottling liquids or semiliquids; Filling jars or cans with liquids or semiliquids using bottling or like apparatus
- B67C3/22—Details
- B67C3/24—Devices for supporting or handling bottles
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/06—Metal compounds
- C10M2201/062—Oxides; Hydroxides; Carbonates or bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/021—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/022—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms containing at least two hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/107—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of two or more specified different alkylene oxides covered by groups C10M2209/104 - C10M2209/106
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
- C10M2229/02—Unspecified siloxanes; Silicones
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/18—Anti-foaming property
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/38—Conveyors or chain belts
Definitions
- This invention relates to aqueous compositions useful in filling and conveying articles.
- the invention also relates to conveyor systems and containers wholly or partially coated with such aqueous compositions.
- Carbonated soft drinks are manufactured by combining soft drink concentrate, cold water, and carbon dioxide and then packaging the composition in bottles or cans.
- the filled container will be transported away from the filler on automated conveyors, may have a label applied, will be inserted into secondary packaging which can be crates, polymer rings, paperboard cartons, or shrink wrapped trays, and finally will be assembled into palletized loads ready for storage and shipping.
- secondary packaging can be crates, polymer rings, paperboard cartons, or shrink wrapped trays, and finally will be assembled into palletized loads ready for storage and shipping.
- aqueous compositions such as rinse water and water based conveyor lubricants.
- aqueous composition refers to compositions that comprise greater than about 90% by weight of water, and includes water, treated water, and water to which one or more functional ingredients have been added.
- Treated water includes water that has been processed to improve some quality of the water, for example water processed to reduce the concentration of impurities and dissolved materials or to reduce the concentration of viable microorganisms.
- “Aqueous composition” includes, but is not limited to bottle rinse water, bottle warmer water, case washer water, and lubricant compositions having water as part of the composition. Because containers are filled at high rates up to and exceeding thousands of containers per minute, some spilling of beverage is likely, especially in the case of carbonated beverages which may foam. Containers frequently will be rinsed immediately downstream of the filler to remove spillage.
- containers are filled with ice cold beverage, it is typically required to rinse them with a warm water rinse in order to raise the temperature of their contents to a value above the dew point, thereby minimizing condensation inside secondary packaging such as boxes or shrink wrap enclosures. Therefore, containers will usually be rinsed a second time in a so called bottle warmer or can warmer. To facilitate rapid movement of beverage containers at speeds up to thousands of containers per minute and higher, it is conventionally required to apply lubricant compositions to the bottle or conveyor surfaces.
- Preferred containers for carbonated soft drinks are thermoplastic bottles made from polyethylene terephthalate (PET). Polyester resins including PET are hydrolytically susceptible, meaning they can react with water in a process known as hydrolysis.
- hydrolysis comes from the Latin roots “hydro” and “lyso” meaning to break apart with water. In this process, water reacts with PET to create two new chain ends and the PET polymer chain is cut. Polymer under stress is much more reactive with regard to hydrolysis, and amorphous PET like that found in parts of carbonated soft drink bottles is more susceptible to hydrolysis than crystalline or oriented PET. Polymer residing at the bottom of carbonated soft drink bottles near the "gate scar” is under stress from the carbonation and is also amorphous, so it is particularly susceptible to hydrolysis. The gate scar is a round bump in the center of the bottom of every PET beverage bottle which is an artifact of the bottle manufacturing process.
- a test tube shaped "preform" that will later be heated and inflated inside of a mold of the final bottle shape is made by injection molding.
- a short stem of PET remains attached to the bottom of the test tube, and when this stem is cut, the gate scar is left as a round stub.
- the gate scar is typically withdrawn slightly from bottom most portion of a PET beverage bottle, and for a bottle standing on a flat table, the gate scar will be about 0.05 to 0.15 inches above the table surface.
- Stress cracking Hydrolysis of PET in carbonated soft drink bottles that proceeds to the point of bottle failure is known as "stress cracking.”
- failure it is meant that one or more cracks propagate through the wall of the bottle and there is a loss of liquid contents. Bottles which fail by stress cracking and bottles nearby which are wetted with spilled beverage become unsellable, and stress cracking can lead to substantial losses of merchandise and productivity.
- the problem of stress cracking in PET bottles filled with carbonated soft drinks has not been well understood. Many investigations have studied stress cracking indirectly. That is, instead of measuring the relative rate of failure, they have measured some property that is believed to correlate with the tendency towards failure such as appearance, time to failure, or rupture stress for samples in contact with chemical compositions.
- ISO 6252 1992(E), "Plastics - Determination of environmental stress cracking (ESC) - Constant-tensile- stress method" available from the International Organization for Standardization (ISO).
- ISO 6252 test polymer strips are subjected to a constant tensile force corresponding to a stress lower than the yield stress while submerged in a test liquid, and the time or stress at which the strip breaks is recorded. It has often been preferred to use one of these or other indirect test methods to predict failure rates rather than measure failure rates of bottles directly. Indirect test methods are relatively simpler and less expensive to conduct.
- PET “compatibility” is determined directly by measuring the actual failure rate of bottles in conditions similar to those in bottle filling and storage, for example by using the PET Stress Crack Test described below.
- bicarbonate alkalinity is the most common type of alkalinity found in water sources, while hydroxide alkalinity is usually absent or present at relatively insignificant levels of less than one percent of the total of hydroxide plus bicarbonate plus carbonate alkalinity.
- the sum of hydroxide, carbonate, and bicarbonate alkalinity of water which is allowed to contact PET bottles in bottling plants typically ranges between about 10 ppm and 100 ppm, expressed as ppm of CaCO 3 (calcium carbonate), with occasional values above 100 ppm.
- the International Society of Beverage Technologists (ISBT) web site strongly recommends to keep the total alkalinity level (expressed as CaCOs) below 50 mg/L (equivalent to 50 ppm) in all water that could potentially contact the bottle (including, but not limited to: lube makeup water, rinser water, warmer water, case washer, etc) in order to minimize the risk of stress crack failure.
- the PET Stress Crack Test in the examples section, water within the ISBT guideline containing 50 ppm or even 25 ppm of bicarbonate alkalinity (expressed as CaCOs) will still give significant amounts of failure, in comparison to deionized or distilled water, which will give no failure.
- Purification of water that contacts PET bottles may be done using processes including ion exchange, lime/lime soda softening, split stream softening, and membrane separation processes such as reverse osmosis and nanofiltration.
- bottles that contact water with the ISBT recommended limit of alkalinity at 50 ppm as CaCO 3 will exhibit significantly more failure than bottles that have only contacted deionized or distilled water.
- Alkalinity is not monitored and controlled in all bottling facilities and in case the alkalinity level increases (for example due to equipment failure) it is beneficial to have other means for mitigating the risk of alkaline induced stress cracking.
- Conveyor lubricant compositions can be effective to erase the effects of alkalinity in the lubricant composition itself and alkalinity that contacted the bottle in a previous rinse step.
- Conveyor lubricant composition that mitigates water alkalinity to be effective at reducing failure due to residual alkalinity from bottle rinsing, it must be applied to bottles downstream of the point of application of the rinse. Effective application of a conveyor lubricant downstream of rinsers and warmers requires the lubricant to contact the susceptible gate scar region.
- this region rides about 0.05 to 0.15 inches above the conveyor surface, in order for the lubricant to make contact, it must be sprayed directly on each bottle or it must be of sufficient depth on the conveyor. In practice, sufficient depth of the lubricant composition on conveyors downstream of rinsers and warmers is provided by foaming the lubricant. In this case, the lubricant must have a tendency to foam.
- the tendency of a lubricant to foam can be determined using a Foam Profile Test as described below. According to this test, non-foaming lubricants have a foam profile less than about 1.1, moderately foaming lubricants have a foam profile between about 1.1 and 1.4, and foaming lubricants have a foam profile value greater than about 1.4.
- Non-foaming lubricants have generally not been used with stress crack susceptible PET packaging in the case that aqueous rinse compositions contain greater than about 50 ppm alkalinity as CaCC> 3 because of the inability to reach the gate scar region of the bottle.
- Newer and particularly preferred conveyor lubricants including silicone emulsion based lubricants are non-foaming.
- Non-foaming silicone based lubricants will not contact the gate portion of the bottle and some other means is required to lessen the risk of stress cracking resulting from contact of bottles with aqueous rinse compositions that contain alkalinity.
- Silicone based lubricants are preferred lubricants for PET bottles because they provide improved lubrication properties and significantly increased conveyor efficiency. Silicone containing lubricant compositions are described, for example in US Patent 6,495,494 (Li et al which is incorporated by reference herein in its entirety).
- conveyor lubricants are "dry" lubricants as described in US Patent Application S/N 11/351,863 titled DRY LUBRICANT FOR CONVEYING CONTAINERS, filed on February 10, 2006 which is incorporated by reference herein in its entirety. Dry lubricants include those that are dispensed onto conveyors in a neat undiluted form, those that are applied to the conveyor intermittently, and/or those that leave the conveyor with a dry appearance or are dry to the touch. In the case of dry lubricants, the lubricant will not contact the stress crack susceptible gate portion on the majority of bottles processed.
- additives described in US Patent Applications S/N 11/233,596 and S/N 11/233,568 may modify the lubrication properties and may result in a pH for the composition that is low relative to compositions without additives. If added in large amounts, addition of components to improve PET compatibility as described in US Patent Applications S/N 11/233,596 and S/N 11/233,568 may result in reduced stability of the resulting composition in the case that the composition comprises an emulsion. Therefore, there exists an opportunity for improving the combination of PET compatibility and other properties of silicone based conveyor lubricants.
- the rising cost of petrochemicals, including raw materials used to make PET creates an incentive to minimize the amount of PET in every beverage bottle.
- the practice of minimizing the amount of PET used in a beverage bottle design is called lightweighting.
- Increased cost of petrochemicals will also provide motivation to use polymers from renewable sources such as agricultural feedstocks.
- Poly(lactic acid) (PLA) is derived from agricultural sources and like PET, is a polyester that can hydrolyze with water. Improving the compatibility between aqueous compositions used during filling and conveying of bottles and hydrolysis susceptible polymers can facilitate the practice of lightweighting, allow a reduction in the mass of polymer used per bottle, and facilitate the use of new polymers including those derived from renewable sources.
- PET post consumer recycled
- PET may include other resins, polyester resins other than PET such as glycol modified PET (also known as PETG or poly ethylene terephthalate glycol copolyester), and impurities such as colorants, catalysts, and remnants of active and passive barrier materials.
- glycol modified PET also known as PETG or poly ethylene terephthalate glycol copolyester
- impurities such as colorants, catalysts, and remnants of active and passive barrier materials.
- PCR PET PCR PET
- a greater PCR polymer content in beverage bottles may be allowable by improving the PET compatibility of aqueous compositions that contact PET bottles during filling and conveying.
- barrier layers in PET bottles which minimize the egress diffusion of carbon dioxide and ingress diffusion of oxygen. Active barrier materials are those that react with the diffusing species, and passive barriers are those that impede the diffusion of the diffusing species without reaction. While externally applied barrier layers can potentially provide a layer of protection for the underlying PET, use of barrier layers can also increase susceptibility towards stress cracking. For example, barrier layers will generally allow the use of lighter weight bottles.
- Barrier layers which slow the egress diffusion of carbon dioxide can allow a higher pressure differential to be maintained between the inside and outside of the bottle resulting in greater tensile stress on the bottle wall, and may diminish the concentration of carbon dioxide at the exterior surface of the PET bottle wall, effectively raising the local pH and thereby increasing the rate of hydrolytic degradation of PET. Improving the PET compatibility of aqueous compositions which contact bottles may be important to diminish the incidence of stress cracking in PET bottles which comprise a barrier layer. [0016] It is against this background that the present invention has been made.
- aqueous compositions have improved compatibility with PET in the case that they contain hardness elements.
- hardness elements metal elements that form metal ions (hardness ions) that go on to form relatively insoluble carbonate compounds, i.e. having solubility products for the carbonate compounds less than about 10 "4 (moles/liter) 2 .
- hardness ions include Ca 2+ , Mg 2+ , Zn 2+ , Fe 2+ , Mn 2+ , and Cu 2+ .
- the concentration of hardness elements is sufficient that there is at least about one ppm of hardness (expressed as CaCOs) in the composition for each ppm of alkalinity (expressed as CaCOs) in the aqueous composition.
- the ratio of hardness (expressed as CaCO 3 ) to alkalinity (expressed as CaCO 3 ) is 1 to 1, 1.1 to 1, 1.2 to 1, 1.5 to 1, and 2.0 to 1.
- the alkalinity level is 50 ppm as CaCO 3
- the aqueous compositions will comprise hardness equivalent to 50, 55, 60, 15 or 100 ppm as CaCO 3 .
- the present invention provides, in one aspect, a method for processing and transporting hydrolytically susceptible polymer bottles filled with carbonated beverages along a conveyor wherein the bottle contacts one or more aqueous compositions having greater than about 50 ppm alkalinity as CaCO 3 , and a ratio of hardness as ppm CaC ⁇ 3 to alkalinity as ppm CaCO 3 equal to at least about 1:1, wherein the passage of bottles is lubricated using a non-foaming conveyor lubricant composition.
- the present invention provides, in another aspect, method for processing and transporting hydrolytically susceptible polymer bottles filled with carbonated beverages along a conveyor wherein the bottle contacts one or more aqueous compositions having a ratio of hardness as ppm CaCO 3 to alkalinity as ppm CaCO 3 equal to at least about 1:1, wherein the passage of bottles is lubricated using a dry lubricant composition.
- the present invention provides, in another aspect, an aqueous lubricant composition comprising a silicone emulsion and greater than about 50 ppm alkalinity as CaCO 3 wherein the lubricant composition has a ratio of hardness as ppm CaCO 3 to alkalinity as ppm CaC ⁇ 3 equal to at least about 1:1.
- the present invention provides, in another aspect, an aqueous lubricant composition comprising between about 0.1 and 1.0 weight percent lubricant concentrate composition and between 99.0 and 99.9 percent dilution water and having greater than about 50 ppm alkalinity as CaCO 3 , wherein the lubricant composition comprises at least one part hardness as ppm CaCO 3 for every part of alkalinity as ppm CaCO 3 in the dilution water.
- the present invention provides, in another aspect an aqueous lubricant composition comprising a silicone emulsion and greater than about 50 ppm hardness as CaCO 3 .
- the present invention provides, in another aspect, a lubricant concentrate composition comprising greater than about 10,000 ppm hardness as CaCO 3 .
- an aqueous rinse composition includes any aqueous composition comprising greater than about 90 percent by weight of water which is applied to bottles in such a way as to essentially wet the majority of the bottle surface.
- Aqueous rinse compositions may be used for reasons including to remove spilled beverage, to prevent scuffing, to facilitate movement of the bottles along the conveyor system, or to raise or lower the temperature of bottle contents.
- the present invention provides, in another aspect, a method for processing and transporting hydrolytically susceptible polymer bottles filled with carbonated beverages along a conveyor wherein the bottle contacts one or more aqueous compositions having a ratio of hardness as ppm CaCO 3 to alkalinity as ppm CaCO 3 equal to at least about 1:1, wherein the bottles are capable to contain at least 20 ounces of beverage and the empty bottles weigh less than about 24 grams per bottle.
- the present invention provides, in another aspect, a method for processing and transporting hydrolytically susceptible polymer bottles filled with carbonated beverages along a conveyor wherein the bottle contacts one or more aqueous compositions having a ratio of hardness as ppm CaCO 3 to alkalinity as ppm CaCO 3 equal to at least about 1:1, wherein the bottles comprise greater than about 10% by weight of a polymer other than PET.
- the present invention provides, in another aspect, a method for processing and transporting hydrolytically susceptible polymer bottles filled with carbonated beverages along a conveyor wherein the bottle contacts one or more aqueous compositions having a ratio of hardness as ppm CaCO 3 to alkalinity as ppm CaCO 3 equal to at least about 1:1, wherein the bottles comprise greater than about 12% by weight of PCR polymer content.
- the present invention provides, in another aspect, a method for processing and transporting hydrolytically susceptible polymer bottles filled with carbonated beverages along a conveyor wherein the bottle contacts one or more aqueous compositions having a ratio of hardness as ppm CaCO 3 to alkalinity as ppm CaCO 3 equal to at least about 1:1, wherein the bottles comprise an active or a passive barrier material.
- the present invention provides, in another aspect, a method for processing and transporting hydrolytically susceptible polymer bottles filled with carbonated beverages along a conveyor wherein the bottle contacts one or more aqueous compositions in which the ratio of hardness as ppm CaCC> 3 to bicarbonate alkalinity as ppm CaCO 3 is at least about 1.5:1.
- the invention provides aqueous compositions useful in the filling and conveying of containers wherein the aqueous composition includes hardness elements.
- Aqueous compositions according to the present invention may be useful to rinse containers thereby removing spilled beverages or effecting an increase in the temperature of the container contents.
- aqueous compositions according to this invention may be useful to reduce the coefficient of friction between conveyor parts and containers and thereby facilitate movement of containers along a conveyor line.
- aqueous compositions of this invention may in some other way improve the efficiency of package processing or a property of the filled package.
- the source of hardness elements in aqueous compositions may be impurities in the water itself or water used to prepare the aqueous composition, or the source of hardness elements may be intentionally added salts of hardness elements, or the source of hardness elements may be a combination of intentionally added hardness element salts and impurities in the water or water used to prepare aqueous compositions and lubricant compositions.
- a majority of the hardness element concentration may be intentionally added, for example as a constituent of a rinse concentrate or a lubricant concentrate and a minority may be provided by the water used to prepare the aqueous composition.
- greater than about 90 percent of the hardness in the final composition or greater than about 70 percent of the hardness in the final composition may be provided by a concentrate composition and less than about 10 percent of the hardness or less than 30 percent of the hardness may be provided by water used to dilute the concentrate.
- greater than about 10 percent of the hardness element concentration or greater than 30 percent of the hardness element concentration in the final aqueous composition may be provided by the water used to prepare the aqueous composition and less than about 90 percent of the hardness element concentration or less than about 70 percent of the hardness element concentration may be intentionally added.
- Total hardness provided in the water used to prepare the aqueous composition may include “carbonate hardness” and “noncarbonate hardness.” When hardness is numerically greater than the sum of carbonate and bicarbonate alkalinity, that amount of hardness equivalent to the total alkalinity is called “carbonate hardness” while the amount of hardness in excess of this is called “noncarbonate hardness.” Carbonate hardness is attributable to dissolved metal carbonate and bicarbonate salts while noncarbonate hardness is usually attributable to dissolved metal sulfates and chlorides. Moderate to high hardness water (50 ppm to 300 ppm) is typically associated with soils formed in limestone (CaCOs) deposited watersheds.
- CaCOs limestone
- Hardness of aqueous compositions can be determined by calculation according to the methods on page 2-36 of Standard Methods for the Examination of Water and Wastewater, 18 th Edition 1992 (Eds. Greenberg, A. E., Clesceri, L. S., and Eaton, A. D.)- According to this method, hardness is computed from separate determinations of hardness elements.
- the concentration of hardness elements may be determined by an analytical method such as atomic absorption (AA) or inductively coupled plasma (ICP) spectroscopy, or it may be known from formulation data.
- Concentration of hardness elements present in aqueous compositions can also be determined for example by analytical methods including titration with a complexing agent as described on page 2-36 Standard Methods for the Examination of Water and Wastewater, 18 th Edition.
- the titration for hardness in aqueous compositions can be done using ethylene diamine tetraacetic acid (EDTA) as a complexing agent and either Eriochrome Black T or 3-hydroxy-4-(6-hydroxy-m- tolylazo) naphthalene-1 -sulfonic acid (Calmagite) as a visible indicator. It is not desirable to use an inhibitor for the titration so that hardness elements such as zinc will titrate as hardness.
- EDTA ethylene diamine tetraacetic acid
- Calmagite 3-hydroxy-4-(6-hydroxy-m- tolylazo) naphthalene-1 -sulfonic acid
- aqueous compositions 1000 g can be titrated from the wine-red to blue color change of Calmagite using a 0.13 molar solution of disodium EDTA.
- the total alkalinity in aqueous compositions can be classified as bicarbonate, carbonate, and hydroxide alkalinity based on results of titration to pH 8.3 (phenolphthalein endpoint) and pH 4.0 (total alkalinity endpoint) as described on pages 2-27 and 2-28 of Standard Methods for the Examination of Water and Wastewater, 18 th Edition.
- the total alkalinity of the compositions in the Examples herein can be calculated by formulation.
- a product of the reaction of hardness ion with bicarbonate ion is a metathesis product salt of the original hardness salt (for example the metathesis product salt in equation (3) above is NaCl)
- the hardness ion salt be selected from the group of hardness ion salts of strong acids with pKa values less than about 3.
- Hardness ion salts of weaker acids with pKa values greater than about 3 are believed to be less preferred because the precipitation reaction may yield more basic and possibly less compatible salt products.
- Preferred hardness salts include halides, nitrates, alkyl and aryl sulfonates such as methane sulfonate and para toluene sulfonate, and sulfates.
- Hardness ions present in aqueous compositions may also be in the form of bicarbonate salts, especially in the case that the source of hardness ions are impurities in the source water.
- precipitation of carbonate salts of hardness ions may be important in the mechanism whereby the PET compatibility of aqueous compositions is improved, it is not required and in fact it is not preferred for precipitation of carbonate salts to occur in use compositions as distributed or dispensed.
- use composition means a composition as it is applied to the bottle or conveyor system. Precipitation of carbonate salts in use compositions may cause problems in distribution or dispensing, for example clogging of filters or spray nozzles. On the other hand, compatibilization of relatively dilute solutions of bicarbonate alkalinity is not required, as concentrations of sodium bicarbonate at concentrations up to and exceeding 525 ppm (313 ppm alkalinity as CaCOs) do not cause failure of PET bottles unless evaporation is allowed to occur.
- the failure rate is zero percent.
- Example 11 the concentration of magnesium ions is 2 x 10 "3 moles/liter and the concentration of bicarbonate ion is also 2 x 10 "3 moles/liter.
- the concentration of calcium ions is 1.6 x 10 "3 moles/liter and the concentration of bicarbonate ion is 5.2 x 10 ⁇ 3 moles/liter.
- Another potential mechanism of improved compatibility in the presence of hardness elements may be interaction of hardness metal ions with carboxylate end groups on the polymer. It is believed that PET polymer chains with carboxylate chain ends may cause autocatalytic hydrolysis of the PET polymer chain. For example a deprotonated carboxylic acid chain end may promote hydrolysis of other ester linkages within the same or adjacent PET polymer chains. Hardness ions that form relatively less soluble carbonates also form relatively less soluble salts with long chain carboxylic acid compounds. The relatively lower solubility of hardness ion salts of PET carboxylate polymer chain ends relative to other cations such as monovalent cations may slow the rate of hydrolytic polymer autocatalysis.
- compositions of the present invention comprise a sufficient concentration of one or more hardness ions to improve the compatibility of the composition with PET.
- the present invention is directed to including hardness elements in the compositions, rather than sequestering them out, the present invention can be, in some embodiments, substantially free of sequestering agents and chelating agents.
- the concept of adding hardness is contrary to conventional practices which are to avoid or sequester hardness elements, the use of hardness to improve PET compatibility of aqueous compositions has proven to be very effective.
- PLA poly(lactic acid)
- PET poly(lactic acid)
- PLA is considered a "sustainable" alternative to petroleum based products including PET, since it is derived from the fermentation of agricultural products such as corn or other sugar or starch rich crops such as sugar beets or wheat.
- PLA is a polyester and contains ester linkages which are subject to cleavage by hydrolysis.
- compositions of the present invention may advantageously be used with containers made of polymeric materials that hydrolyze under alkaline conditions including PET and PLA in in the form of both non-refillable (e.g. so called “one-way” bottles) as well as refillable (e.g. so called “Ref-PET”) containers.
- containers made of polymeric materials that hydrolyze under alkaline conditions including PET and PLA in in the form of both non-refillable (e.g. so called “one-way” bottles) as well as refillable (e.g. so called “Ref-PET”) containers.
- the present invention provides, in one aspect, a method for rinsing containers comprising applying an aqueous composition to the container wherein the aqueous composition comprises hardness ions in an amount sufficient to provide a value of hardness as ppm CaCO 3 that is equal to at least about the value of alkalinity as ppm CaCC> 3 .
- the aqueous composition comprises hardness ions in an amount sufficient to provide a value of hardness as ppm CaCO 3 that is equal to at least about the value of alkalinity as ppm CaCC> 3 .
- aqueous compositions useful for rinsing bottles advantageously include sanitizing agents.
- Useful sanitizing agents include quaternary ammonium compounds or peracetic acid and include commercial products such as STER-BAC, Cooling Care 2065, SURPASS 100, and SURPASS 200 available from Ecolab, St. Paul, MN.
- Aqueous rinse compositions comprising a sanitizer according to the present invention may be prepared by diluting a sanitizing concentrate such as STER-BAC, Cooling Care 2065, SURPASS 100, and SURPASS 200 with hard water, or may be prepared by adding to water both a sanitizing concentrate plus a compatibility improving concentrate, wherein the compatibility improving concentrate comprises one or more salts of hardness ions.
- a sanitizing concentrate such as STER-BAC, Cooling Care 2065, SURPASS 100, and SURPASS 200 with hard water
- a compatibility improving concentrate comprises one or more salts of hardness ions.
- Aqueous compositions of the present invention that are used for rinsing can be applied undiluted or may be diluted before use. It may be desirable to provide compositions of the present invention in the form of concentrates that can be diluted with water at the point of use to give aqueous use compositions.
- use composition means a composition as it is applied to the bottle or conveyor system and "concentrate” means a composition that is diluted with water and/or a hydrophilic diluent to give a use composition.
- inventive rinse concentrate compositions therefore comprise sufficient concentrations of hardness ions such that when one part of the concentrate composition is diluted with between 200 and 10,000 parts of water and/or a hydrophilic diluent to give a use composition, the ratio of the total hardness of the composition (expressed as ppm CaCO 3 ) to the total alkalinity of the composition (expressed as ppm CaCC ⁇ ) is greater than about 1 to 1 while the total alkalinity of the composition is greater than about 50 ppm as CaCO 3 .
- inventive rinse concentrate compositions comprise hardness of at least about 10,000 ppm as CaCO 3 , at least about 15,000 ppm as CaCC> 3 , or at least about 20,000 ppm as CaCO 3 .
- Rinse concentrates according to the present invention may be liquid, semi-solid, or solid.
- the present invention provides, in another aspect, a method for lubricating the passage of a container along a conveyor comprising applying a composition of an aqueous lubricant composition to at least a portion of the container contacting surface of the conveyor or to at least a portion of the conveyor-contacting surface of the Container wherein the lubricant composition comprises greater than about one part hardness as ppm CaCO 3 for every part alkalinity as ppm CaC ⁇ 3 .
- Preferred conveyor lubricant compositions include compositions based on silicone materials, fatty amines, nonionic surfactants, and other materials that may be .formulated to contain hardness ions.
- Lubricant materials that are not useful in the compositions of the present invention include those that are "incompatible" with hardness ions or form precipitates in the presence of hardness ions such as fatty acid lubricants and phosphate ester lubricants.
- Lubricant compositions of the present invention can be applied as is or may be diluted before use. It may be desirable to provide compositions of the present invention in the form of concentrates that can be diluted at the point of use to give use compositions. If diluted, preferred ratios for dilution at the point of use range from about 1:200 to 1:1000 (parts of concentrate: parts of diluent).
- Inventive lubricant concentrate compositions therefore comprise sufficient concentrations of hardness ions such that when one part of the concentrated aqueous concentration is diluted with between 200 and 10,000 parts of water and/or hydrophilic diluent to give a use composition, the ratio of the total hardness of the composition (expressed as ppm CaCO 3 ) to the total alkalinity of the composition (expressed as ppm CaCOa) is greater than about 1 to 1 while the total alkalinity of the composition is greater than about 50 ppm as CaC ⁇ 3 . Accordingly, concentrate compositions comprise hardness of at least about 10,000 ppm as CaCO 3 , at least about 15,000 ppm as CaCO 3 , or at least about 20,000 ppm as CaC ⁇ 3 .
- Lubricant concentrates according to the present invention may be liquid, semi-solid, or solid.
- Preferred silicone lubricant compositions comprise one or more water miscible silicone materials, that is, silicone materials that are sufficiently water- soluble or water-dispersible so that when added to water at the desired use level they form a stable solution, emulsion, or suspension.
- a variety of water-miscible silicone materials can be employed in the lubricant compositions, including silicone emulsions (such as emulsions formed from methyl (dimethyl), higher alkyl and aryl silicones; and functionalized silicones such as chlorosilanes; amino-, methoxy-, epoxy- and vinyl-substituted siloxanes; and silanols).
- Suitable silicone emulsions include E2175 high viscosity polydimethylsiloxane (a 60% siloxane emulsion commercially available from Lambent Technologies, Inc.), E2140 polydimethylsiloxane (a 35% siloxane emulsion commercially available from Lambent Technologies, Inc.), E2140 FG food grade intermediate viscosity polydimethylsiloxane (a 35% siloxane emulsion commercially available from Lambent Technologies, Inc.), HV490 high molecular weight hydroxy-terminated dimethyl silicone (an anionic 30-60% siloxane emulsion commercially available from Dow Corning Corporation), SM2135 polydimethylsiloxane (a nonionic 50% siloxane emulsion commercially available from GE Silicones) and SM2167 polydimethylsiloxane (a cationic 50% siloxane emulsion commercially available from GE Silicones).
- Other water-mi scible silicone materials include finely divided silicone powders such as the TOSPEARLTM series (commercially available from Toshiba Silicone Co. Ltd.); and silicone surfactants such as SWP30 anionic silicone surfactant, WAXWS-P nonionic silicone surfactant, QUATQ-400M cationic silicone surfactant and 703 specialty silicone surfactant (all commercially available from Lambent Technologies, Inc.).
- Suitable silicone emulsions and other water- miscible silicone materials are listed in aforementioned US Patent Applications S/N 11/233,596 and S/N 11/233,568 which are incorporated herein by reference in their entirety.
- Polydimethylsiloxane emulsions are preferred silicone materials.
- concentration of the active silicone material useful in the present invention exclusive of any dispersing agents, water, diluents, or other ingredients used to emulsify the silicone material or otherwise make it miscible with water falls in the range of about 0.0005 wt. % to about 10 wt. %, preferably 0.001 wt. % to about 8 wt. %, and more preferably 0.002 wt. % to about 5 wt. %.
- the concentration of active silicone material useful in the present invention exclusive of any dispersing agents, water, diluents, or other ingredients used to emulsify the silicone material or otherwise make it miscible with water falls in the range of about 0.05 wt. % to about 20 wt. %, preferably 0.10 wt. % to about 5 wt. %, and more preferably 0.2 wt. % to about 1.0 wt. %.
- Preferred lubricant compositions are substantially aqueous that is, they comprise greater than about 90% of water.
- Lubricant compositions of the present invention may be "dry" lubricants as described in aforementioned US Patent Application S/N 11/351,863 which is incorporated by reference herein in its entirety. Dry lubricants include those that are dispensed onto conveyors in a neat undiluted form, those that are applied to the conveyor intermittently, and/or those that leave the conveyor with a dry appearance or are dry to the touch. Preferred "dry" lubricants comprise a silicone material, water or a combination of water plus hydrophilic diluent, and optionally a water miscible lubricant as described in US Patent Application S/N 11/351,863.
- Preferred amounts for the silicone material, water miscible lubricant and water or hydrophilic diluent are about 0.1 to about 10 wt. % of the silicone material (exclusive of any water or other hydrophilic diluent that may be present if the silicone material is, for example, a silicone emulsion), about 0 to about 20 wt. % of the water miscible lubricant, and about 70 to about 99.9 wt. % of water or hydrophilic diluent. More preferably, the lubricant composition contains about 0.2 to about 8 wt. % of the silicone material, about 0.05 to about 15 wt. % of the water miscible lubricant, and about 75 to about 99.5 wt.
- the lubricant composition contains about 0.5 to about 5 wt. % of the silicone material, about 0.1 to about 10 wt. % of the hydrophilic lubricant, and about 85 to about 99 wt. % of water or hydrophilic diluent.
- the lubricant compositions may also contain a wetting agent. Silicone lubricant compositions that comprise a wetting agent and have improved compatibility with PET are disclosed in aforementioned US Patent Application S/N 11/233,596 titled SILICONE LUBRICANT WITH GOOD WETTING ON PET SURFACES. In some embodiments, the lubricant compositions may also contain a stoichiometric amount of an organic acid.
- Lubricant compositions that comprise a stoichiometric amount of an organic acid and have improved compatibility with PET are disclosed in aforementioned US Patent Application S/N 11/233,568 titled SILICONE CONVEYOR LUBRICANT WITH STOICHIOMETRIC AMOUNT OF AN ORGANIC ACID.
- Fatty amine conveyor lubricant compositions useful in the present invention include compositions based on fatty diamine compounds as disclosed in US Patent 5,182,035 and US Patent 5,510,045 and alkyl ether amine compounds as disclosed in US Patent 5,723,418 and US Patent 5,863,874, all of which are incorporated herein by reference in their entirety.
- Preferred fatty amine lubricant compositions contain an effective lubricating amount of one or more amine compounds including diamine acetates having the formula [R 1 NHR 2 NHy + (CH 3 CO 2 ) " or [R 1 NH 2 R 2 NH3] 2+ (CH 3 CO 2 )2 ' wherein R 1 is a Ci 0 - Ci 8 aliphatic group or a partially unsaturated Cio - C 18 aliphatic group and R 2 is a C 1 - C 5 alkylene group and fatty monoamine acetates having the formula [R 1 R 3 R 4 NH] + (CHa CO2) " wherein R 1 is a C 1O - C 18 aliphatic group or a partially unsaturated Cio — C 1S aliphatic group, and R 3 and R 4 are independently selected from H and CH 3 .
- Particularly preferred fatty amine lubricant compositions contain one or more of oleyl propylene diamine diacetate, coco alkyl propylene diamine diacetate, and lauryl dimethyl amine acetate.
- Preferred fatty amine lubricant compositions may also include nonionic surfactants such as alcohol ethoxylates, chlorine, methyl, propyl or butyl end capped alcohol ethoxylates, ethoxylated alkyphenol compounds, and poly(ethylene oxide - propylene oxide) copolymers.
- Preferred ethoxylate compound conveyor lubricants include compositions based on one or more of the group including alcohol ethoxylates, chlorine, methyl, propyl or butyl end capped alcohol ethoxylates, ethoxylated alkyphenol compounds, and poly(ethylene oxide — propylene oxide) copolymers as disclosed in US Patent 5,559,087 which is incorporated herein by reference in its entirety.
- Particularly preferred ethoxylate compound conveyor lubricants have a cloud point for the composition greater than about 100°F. Ethoxylate compounds with relatively lower cloud points may be advantageously used in combination with other ethoxylate compounds with higher cloud points, hydrotropes such as alkyl aryl sulfonate compounds, and other so called coupling agents.
- Lubricant compositions which comprise a plurality of materials which improve the PET compatibility including hardness ions, stoichiometric amounts of acid, and wetting agents may exhibit a synergistic effect, that is, the overall reduction of the failure rate for PET bottles may be greater than the sum of the reduction of the failure rate for either a stoichiometric amount of acid, wetting agent, or hardness element acting alone.
- the lubricant compositions can contain functional ingredients if desired.
- the compositions can contain hydrophilic diluents, antimicrobial agents, stabilizing/coupling agents, detergents and dispersing agents, anti-wear agents, viscosity modifiers, corrosion inhibitors, film forming materials, antioxidants or antistatic agents.
- hydrophilic diluents for example, hydrophilic diluents, antimicrobial agents, stabilizing/coupling agents, detergents and dispersing agents, anti-wear agents, viscosity modifiers, corrosion inhibitors, film forming materials, antioxidants or antistatic agents.
- the present invention may in some embodiments substantially exclude sequestering agents or chelating agents.
- Preferred lubricant compositions may be foaming, that is, they may have a foam profile value greater than about 1.1 when measured using a Foam Profile Test.
- a Foam Profile Test is disclosed in the aforementioned US Patent Application S/N 11/233,596 titled SILICONE LUBRICANT WITH GOOD WETTING ON PET SURFACES and in the present invention.
- the lubricant compositions preferably create a coefficient of friction (COF) that is less than about 0.20, more preferably less than about 0.15, and most preferably less than about 0.12, when evaluated using the Short Track Conveyor Test described below.
- COF coefficient of friction
- a variety of kinds of conveyors and conveyor parts can be coated with the lubricant composition.
- Parts of the conveyor that support or guide or move the containers and thus are preferably coated with the lubricant composition include belts, chains, gates, chutes, sensors, and ramps having surfaces made of fabrics, metals, plastics, composites, or combinations of these materials.
- the lubricant compositions of the present invention are especially designed for use with carbonated soft drink containers but can also be applied to a wide variety of containers including beverage containers; food containers; household or commercial cleaning product containers; and containers for oils, antifreeze or other industrial fluids.
- the containers can be made of a wide variety of materials including glasses; plastics (e.g., polyolefins such as polyethylene and polypropylene; polystyrenes; polyesters such as PET and polyethylene naphthalate (PEN); polyamides, polycarbonates; and mixtures or copolymers thereof); metals (e.g., aluminum, tin or steel); papers (e.g., untreated, treated, waxed or other coated papers); ceramics; and laminates or composites of two or more of these materials (e.g., laminates of PET, PEN or mixtures thereof with another plastic material).
- plastics e.g., polyolefins such as polyethylene and polypropylene; polystyrenes; polyesters such as PET and polyethylene naphthalate (PEN); polyamides, polycarbonates; and mixtures or copolymers thereof
- metals e.g., aluminum, tin or steel
- papers e.g., untreated, treated, waxed
- the containers can have a variety of sizes and forms, including cartons (e.g., waxed cartons or TETRAP AKTM boxes), cans, bottles and the like.
- cartons e.g., waxed cartons or TETRAP AKTM boxes
- cans cans
- bottles and the like any desired portion of the container can be coated with the lubricant composition
- the lubricant composition preferably is applied only to parts of the container that will come into contact with the conveyor or with other containers.
- the lubricant composition preferably is applied to the conveyor rather than to the container.
- the lubricant compositions of the present invention can be a liquid or semisolid at the time of application.
- the lubricant composition is a liquid having a viscosity that will permit it to be pumped and readily applied to a conveyor or containers, and that will facilitate rapid film formation whether or not the conveyor is in motion.
- the lubricant composition can be formulated so that it exhibits shear thinning or other pseudo-plastic behavior, manifested by a higher viscosity (e.g., non-dripping behavior) when at rest, and a much lower viscosity when subjected to shear stresses such as those provided by pumping, spraying or brushing the lubricant composition. This behavior can be brought about by, for example, including appropriate types and amounts of thixotropic fillers (e.g., treated or untreated fumed silicas) or other rheology modifiers in the lubricant composition.
- thixotropic fillers e.g., treated or untreated fumed silicas
- Aqueous compositions used for rinsing bottles may be applied to bottles through standard shower heads or spray nozzles.
- Equipment useful for rinsing PET bottles includes Series 600 rinsers available from Uni-Pak, Longwood FL.
- the aqueous composition is preferably recycled in a so called bottle warmer apparatus, for example bottle warmers available from Uni-Pak, Longwood FL.
- Lubricant compositions can be applied in a constant or intermittent fashion.
- the lubricant composition is applied in an intermittent fashion in order to minimize the amount of applied lubricant composition.
- Preferred dry lubricant compositions may be applied for a period of time and then not applied for at least 15 minutes, at least 30 minutes, or at least 120 minutes or longer.
- the application period may be long enough to spread the composition over the conveyor belt (i.e. one revolution of the conveyor belt).
- the actual application may be continuous, i.e. lubricant is applied to the entire conveyor, or intermittent, i.e. lubricant is applied in bands and the containers spread the lubricant around.
- the lubricant is preferably applied to the conveyor surface at a location that is not populated by packages or containers. For example, it is preferable to apply the lubricant upstream of the package or container flow or on the inverted conveyor surface moving underneath and upstream of the container or package.
- a particularly preferred method of application of lubricant compositions including lubricant compositions that are applied intermittently is by spraying through non-energized nozzles, as disclosed in the aforementioned US Patent Application S/N 11/351,863, which is incorporated herein by reference in its entirety.
- the ratio of application time to non-application time may be 1:1, 1:10, 1:30, 1:180, and 1:500 where the lubricant maintains a low coefficient of friction in between lubricant applications.
- a feedback loop may be used to determine when the coefficient of friction reaches an unacceptably high level.
- the feedback loop may trigger the lubricant composition to turn on for a period of time and then optionally turn the lubricant composition off when the coefficient of friction returns to an acceptable level.
- the lubricant coating thickness preferably is maintained at at least about 0.0001 mm, more preferably about 0.001 to about 2 mm, and most preferably about 0.005 to about 0.5 mm.
- Application of the lubricant composition can be carried out using any suitable technique including spraying, wiping, brushing, drip coating, roll coating, and other methods for application of a thin film.
- Improving the PET compatibility of aqueous compositions used during the filling and conveying of PET bottles can facilitate the activity of lightweighting PET bottles, and accordingly, in the presence of aqueous compositions comprising hardness ions, the weight of PET bottle used for a twenty ounce serving of a carbonated soft drink may be reduced from over 25 grams per bottle to less than 25 grams per bottle, less than 24 grams per bottle, and less than 23 grams per bottle.
- Improving the PET compatibility of aqueous compositions used during the filling and conveying of PET bottles can facilitate the use of polymers other than PET, and accordingly, in the presence of aqueous compositions comprising hardness ions, bottles used for carbonated soft drinks may contain greater than 10% by weight of a polymer other than PET. Improving the PET compatibility of aqueous compositions used during the filling and conveying of PET bottles through the incorporation of hardness ions can reduce the risk of stress cracking in the case that PET bottles contain recycled polymer and may allow the PCR polymer content in beverage bottles to be increased to greater than 12%, greater than 15%, and greater than 20%.
- Aqueous compositions of the present invention can if desired be evaluated using a Foam Profile Test, a Short Track Conveyor Test and a PET Stress Crack Test.
- a conveyor system employing a motor-driven 83 mm wide by 6.1 meter long REXNORDTM LF polyacetal thermoplastic conveyor belt was operated at a belt speed of 30.48 meters/minute.
- Four 20 ounce filled PET beverage bottles were lassoed and connected to a stationary strain gauge. The force exerted on the strain gauge during belt operation was recorded using a computer.
- a thin, even coat of the lubricant composition was applied to the surface of the belt using conventional lubricant spray nozzles which apply a total of 3.2 gallons of lubricant composition per hour.
- the belt was allowed to run for 25 to 90 minutes during which time a consistently low drag force was observed.
- Compatibility of aqueous compositions with PET beverage bottles was determined by charging bottles with carbonated water, contacting with the aqueous composition, storing at elevated temperatures and humidity for a period of 28 days, and counting the number of bottles that either burst or leaked through cracks in the base portion of the bottle.
- Standard twenty ounce "contour" bottles (available from Southeastern Container, Enka NC) were charged successively with 557 g of chilled water at 0 to 5°C, 10.6 g of sodium bicarbonate, and 17.1 mL (21.Ig) of 50 weight percent citric acid solution in water.
- test aqueous composition was poured into the bus pan around the bottles so that the total amount of test aqueous composition in the pan (carried in on bottles and poured in separately) was equal to 132 g. The test aqueous compositions were not foamed for this test.
- An aqueous composition consisting of a solution of deionized water containing 100 ppm alkalinity as CaCO 3 was prepared by dissolving 0.168 g of sodium bicarbonate in lOOOg of deionized water.
- the soft alkaline water contained 99.7 ppm total alkalinity as CaCO 3 , ⁇ 0.5 ppm calcium, ⁇ 0.5 ppm magnesium, and total hardness as CaCO 3 equal to ⁇ 1.5 ppm.
- the ratio of hardness as CaCO 3 to alkalinity as CaCO 3 was ⁇ 0.02 to 1.
- the alkaline water aqueous composition was tested for PET compatibility as described above. After 28 days of storage under conditions of 100 0 F and 85% relative humidity, 14 of 96 bottles had failed (15 %). The crazing score for the unfailed bottles in this test was 2.4.
- An aqueous composition which contained 220 ppm of calcium chloride plus 100 ppm alkalinity as CaCO 3 was prepared by diluting 5 g of a 4.4% solution of calcium chloride in water with a solution of 0.168 g of sodium bicarbonate in 995 g of deionized water.
- the resulting aqueous composition contained hardness ion equivalent to 198 ppm hardness as CaCO 3 and the ratio of hardness as CaCC> 3 to alkalinity as CaCC> 3 was 1.98 to 1.
- the calcium chloride containing alkaline aqueous composition was tested for PET compatibility as described above. After 28 days of storage under conditions of 100 0 F and 85% relative humidity, 0 of 96 bottles had failed (0 %).
- the crazing score for the unfailed bottles in this test was 2.1. What this example shows is that adding the salt of a hardness ion to alkaline water to give an aqueous composition with a ratio of hardness to alkalinity equal to 1.98 to 1 is capable to reduce the failure rate of bottles in the PET compatibility test.
- aqueous composition consisting of hard alkaline water from a bottle warmer used for warming PET bottles on a conveyor line using a silicone lubricant was tested for PET compatibility as described above.
- the hard alkaline water sample was titrated to pH 8.3 and pH 4.0 using 0.1 N HCl, whereupon it was found that the sample contained 86.6 ppm bicarbonate alkalinity as CaCO 3 and 0.2 ppm carbonate alkalinity as CaC ⁇ 3 for a total alkalinity equal to 86.8 ppm as CaCO 3 .
- a metals analysis was conducted by inductively coupled plasma (ICP) spectroscopy which showed that the sample contained 32 ppm calcium, 8 ppm magnesium, and total hardness as CaCO3 equal to 115 ppm.
- the ratio of hardness as CaC ⁇ 3 to alkalinity as CaC ⁇ 3 was 1.32 to 1.
- the hard alkaline warmer water was tested for PET compatibility as described above. After 28 days of storage under conditions of 100 0 F and 85% relative humidity, 0 of 96 bottles had failed (0 %). The crazing score for the unfailed bottles in this test was 1.5. What this example shows is that substituting untreated, hard alkaline water with a ratio of hardness to alkalinity equal to 1.32 to 1 for soft alkaline water is capable to reduce the failure rate of bottles in the PET compatibility test.
- EXAMPLE 3 soft alkaline water plus silicone lubricant with magnesium chloride
- a lubricant concentrate composition was prepared by adding 1.50g of a solution of 10% PLURONIC F108 polyethylene oxide-propylene oxide) block copolymer (available from BASF Corporation, Mount Olive, NJ), , 12.5g 30% MgCl 2 , 7.99g KATHON CG-ICP (available from Rohm and Haas Company, Philadelphia, PA), and 2.53 g of Lambent E2140FG silicone emulsion to 75.5g deionized water.
- An aqueous lubricant composition was prepared by diluting 2.5 g of the lubricant concentrate composition with 997.5 g of a solution of 168 ppm sodium bicarbonate in deionized water.
- the resulting lubricant composition contained 94 ppm magnesium chloride (equivalent to 98 ppm hardness as CaCO 3 ) and 168 ppm sodium bicarbonate (equivalent to 100 ppm alkalinity as CaCO ⁇ ).
- the ratio of hardness as CaCO 3 to alkalinity as CaCO 3 was 0.98 to 1.
- the foam profile value for the composition measured as described above was 1.0.
- the lubricant composition was tested for PET compatibility as described above whereupon after 28 days of storage under conditions of 100 0 F and 85% relative humidity, 5 of 96 bottles had failed (5 %). The crazing score for the unfailed bottles in this test was 3.0. What this example shows is that adding a lubricant concentrate composition comprising a hardness ion salt to alkaline water to give a lubricant composition with a ratio of hardness to alkalinity equal to 0.98 to 1 is capable to reduce the failure rate of bottles in the PET compatibility test.
- a lubricant concentrate composition was prepared by adding 0.33 g glacial acetic acid, 1.25g GENAMIN LA302-D (available from Clariant Corporation, Mount Holly, NC), 0.4g of SURFONIC L24-7 surfactant (available from Huntsman Corporation, Houston TX), 15.9g 30% MgCl 2 , 1.25g KATHON CG-ICP, and 1.25g Lambent E2140FG silicone emulsion to 79.6g deionized water.
- aqueous lubricant composition was prepared by diluting 2.5 g of the lubricant concentrate composition with 997.5 g of a solution of 168 ppm sodium bicarbonate in deionized water.
- a mixture of 2500 ppm of lubricant concentrate in deionized water without added alkalinity was titrated with 0.1 N HCl and the total alkalinity calculated as described above was determined to be 12 ppm as CaCO 3 .
- the resulting lubricant composition contained 119 ppm magnesium chloride (equivalent to 125 ppm hardness as CaCO 3 ), 112 ppm total alkalinity as CaCCh, and 168 ppm NaHCO 3 (equivalent to 100 ppm alkalinity as CaCOa) •
- the ratio of hardness to total alkalinity was 1.12 to 1 and the ratio of hardness to alkalinity from the dilution water was 1.25 to 1.
- the foam profile value for the composition measured as described above was 1.0.
- the lubricant composition was tested for PET compatibility as described above whereupon after 28 days of storage under conditions of 100 0 F and 85% relative humidity, 0 of 96 bottles had failed (0 %).
- the crazing score for the unfailed bottles in this test was 3.8. What this example shows is that adding a lubricant concentrate composition comprising the salt of a hardness ion to alkaline water to give a lubricant composition with a ratio of hardness to alkalinity equal to 1.25 to 1 is capable to reduce the failure rate of bottles in the PET compatibility test.
- 20 g of the lubricant concentrate composition was diluted with 3 Kg of the hard alkaline municipal water of Example 7, and 7 Kg of deionized water.
- the coefficient of friction between four 20 ounce "Global Swirl" bottles and Delrin track was 0.13.
- An aqueous composition which contained 136 ppm of zinc chloride plus 100 ppm alkalinity as CaCO 3 was prepared by diluting 10 g of a 1.36% solution of zinc chloride in water with a solution of 0.168 g of sodium bicarbonate in lOOOg of deionized water.
- the resulting aqueous composition contained hardness ion equivalent to 100 ppm hardness as CaCOa and the ratio of hardness as CaC ⁇ 3 to alkalinity as CaCO 3 was 1.00 to 1.
- the zinc chloride containing alkaline aqueous composition was tested for PET compatibility as described above. After 28 days of storage under conditions of 100 0 F and 85% relative humidity, 0 of 96 bottles had failed (0 %).
- the ratio of hardness as CaCC> 3 to alkalinity as CaCC> 3 was 0.95 to 1.
- the hard alkaline municipal water was tested for PET compatibility as described above except that twenty ounce "Global Swirl" bottles were substituted for twenty ounce contour bottles. After 28 days of storage under conditions of 100 0 F and 85% relative humidity, 1 of 96 bottles had failed (1 %). The crazing score for the unfailed bottles in this test was 2.0. What this example shows is that substituting untreated, hard alkaline water with a ratio of hardness to alkalinity equal to 0.95 to 1 for soft alkaline water is capable to reduce the failure rate of bottles in the PET compatibility test.
- An aqueous lubricant composition was prepared which contained 125 ppm Lambent E2140FG silicone emulsion, 7.5 ppm PLURONIC F108 poly(ethylene oxide-propylene oxide) block copolymer, 5.0 ppm methyl paraben, and 168 ppm sodium bicarbonate (equivalent to 100 ppm alkalinity as CaCO ⁇ ).
- the ratio of hardness as CaC ⁇ 3 to alkalinity as CaC ⁇ 3 was ⁇ 0.02 to 1.
- the lubricant composition was tested for PET compatibility as described above except that twenty ounce "Global Swirl" bottles were substituted for twenty ounce contour bottles. After 28 days of storage under conditions of 100 0 F and 85% relative humidity, 9 of 48 bottles (19%) had failed.
- An aqueous lubricant composition was prepared which contained 125 ppm Lambent E2140FG silicone emulsion, 7.6 ppm PLTJRONIC F108 polyethylene oxide-propylene oxide) block copolymer, 5.0 ppm methyl paraben, 220 ppm CaCh (equivalent to 198 ppm hardness as CaCO 3 ) and 168 ppm sodium bicarbonate (equivalent to 100 ppm alkalinity as CaCO 3 ). The ratio of hardness as CaC ⁇ 3 to alkalinity as CaCO 3 was 1.98 to 1. The foam profile value for the composition measured as described above was 1.0.
- the silicone lubricant composition was tested for PET compatibility as described above except that twenty ounce "Global Swirl" bottles were substituted for twenty ounce contour bottles. After 28 days of storage under conditions of 100 0 F and 85% relative humidity, 0 of 96 bottles had failed (0%). The crazing score for the unfailed bottles in this test was 2.6. What this example shows is that adding the salt of a hardness ion to an alkaline silicone containing lubricant composition such that the ratio of hardness to alkalinity is equal to 1.98 to 1 is capable to reduce the failure rate of bottles in the PET compatibility test.
- An aqueous lubricant composition was prepared which contained 125 ppm Lambent E2140FG silicone emulsion, 7.5 ppm PLURONIC F108 polyethylene oxide-propylene oxide) block copolymer, 5.0 ppm methyl paraben, 189 ppm MgCl 2 (equivalent to 198 ppm hardness as CaCCh ) and 168 ppm sodium bicarbonate (equivalent to 100 ppm alkalinity as CaCCb ) ⁇
- the ratio of hardness as CaCO3 to alkalinity as CaCCb was 1.98 to 1.
- the lubricant composition was tested for PET compatibility as described above except that twenty ounce "Global Swirl" bottles were substituted for twenty ounce contour bottles whereupon after 28 days of storage under conditions of 100 0 F and 85% relative humidity, 0 of 96 bottles had failed (0%).
- the crazing score for the unfailed bottles in this test was 4.0. What this example shows is that adding the salt of a hardness ion to an alkaline silicone containing lubricant composition such that the ratio of hardness to alkalinity is equal to 1.98 to 1 is capable to reduce the failure rate of bottles in the PET compatibility test.
- aqueous lubricant composition was prepared which contained 125 ppm Lambent E2140FG silicone emulsion, 7.5 ppm PLURONIC F108 polyethylene oxide-propylene oxide) block copolymer, and 5.0 ppm methyl paraben in municipal water from Eagan, Minnesota.
- the Eagan municipal water contained 261 ppm total alkalinity as CaCO 3 , 64 ppm calcium, 22 ppm magnesium, total hardness as CaCO 3 equal to 249 ppm, and a ratio of hardness as CaCO 3 to alkalinity as CaC ⁇ 3 equal to 0.95 to 1.
- the lubricant composition was tested for PET compatibility as described whereupon after 28 days of storage under conditions of 100 0 F and 85% relative humidity, 0 of 96 bottles had failed (0%). The crazing score for the unfailed bottles in this test was 2.0. What this example shows is that a diluting a silicone lubricant with hard alkaline water is capable to reduce the failure rate of bottles in the PET compatibility test relative to diluting with soft alkaline water.
- An aqueous lubricant composition was prepared which contained 388 ppm PLURONIC F108 poly(ethylene oxide-propylene oxide) block copolymer, 98 ppm ANTAROX BL-240 surfactant (available from Rodia, Cranbury NJ), 48 ppm H 2 O 2 , 98 ppm NEODOL 25-9 surfactant (product of Shell Oil Company, Houston, TX), and 168 ppm sodium bicarbonate (equivalent to 100 ppm alkalinity as CaCO 3 ). The ratio of hardness as CaCO 3 to alkalinity as CaCOs was ⁇ 0.02 to 1.
- the ethoxylate compound lubricant composition was tested for PET compatibility as described above except that twenty ounce "Global Swirl" bottles were substituted for twenty ounce contour bottles, whereupon after 28 days of storage under conditions of 10O.?F and 85% relative humidity, 14 of 96 bottles had failed (15%).
- the crazing score for the unfailed bottles in this test was 7.2.
- An aqueous lubricant composition was prepared which contained 388 ppm PLURONIC F108 poly(ethylene oxide-propylene oxide) block copolymer, 98 ppm ANTAROX BL-240 surfactant, 48 ppm H 2 O 2 , 98 ppm NEODOL 25-9 surfactant, 220 ppm CaCl 2 (equivalent to 198 ppm hardness as CaCO 3 ) and 168 ppm sodium bicarbonate (equivalent to 100 ppm alkalinity as CaCOs). The ratio of hardness as CaCO 3 to alkalinity as CaCO 3 was 1.98 to 1.
- the foam profile value for the composition measured as described above was 1.6.
- the aqueous ethoxylate compound lubricant composition was tested for PET compatibility as described above except that twenty ounce "Global Swirl" bottles were substituted for twenty ounce contour bottles, whereupon after 28 days of storage under conditions of 100 0 F and 85% relative humidity, 0 of 96 bottles had failed (0%).
- the crazing score for the unfailed bottles in this test was 7.4. What this example shows is that adding the salt of a hardness ion to an alkaline ethoxylate compound containing lubricant composition such that the ratio of hardness to alkalinity is equal to 1.98 to 1 is capable to reduce the failure rate of bottles in the PET compatibility test.
- COMPARATIVE EXAMPLE E soft alkaline water plus commercial conveyor lubricant
- An aqueous lubricant composition was prepared by diluting 5.0 g of SMARTFOAM PLUS lubricant concentrate composition (available from Pure- Chem Products Inc., Stanton CA) with 995 g of a solution of 168 ppm sodium bicarbonate in deionized water.
- SMARTFOAM PLUS is described as containing a primary alcohol ethoxylate compound.
- the resulting lubricant composition contained 2500 ppm SMARTFOAM PLUS and 168 ppm sodium bicarbonate (equivalent to 100 ppm alkalinity as CaCOs).
- the ratio of hardness as CaCO 3 to alkalinity as CaCO 3 was ⁇ 0.02 to 1.
- the SMARTFOAM PLUS lubricant composition was tested for PET compatibility. After 28 days of storage under conditions of 100°F and 85% relative humidity, 20 of 96 bottles had failed (21%). The crazing score for the unfailed bottles in this test was 7.9.
- a lubricant concentrate composition was prepared by adding 75 g of deionized water and 25 g of 30% magnesium chloride to lOOg SMARTFOAM PLUS.
- An aqueous lubricant composition was prepared by diluting 5.0 g of the lubricant concentrate composition with 995 g of a solution of 168 ppm sodium bicarbonate in deionized water.
- the resulting lubricant composition contained 2500 ppm SMARTFOAM PLUS, 188 ppm magnesium chloride (equivalent to 197 ppm hardness as CaCO 3 ), and 168 ppm sodium bicarbonate (equivalent to 100 ppm alkalinity as CaCOs).
- the ratio of hardness as CaCO 3 to alkalinity as CaCO 3 was 1.98 to 1.
- the commercial conveyor lubricant plus magnesium chloride composition was tested for PET compatibility as described above. After 28 days of storage under conditions of 100 0 F and 85% relative humidity, 0 of 96 bottles had failed (0%). The crazing score for the unfailed bottles in this test was 7.6. What this example shows is that adding the salt of a hardness ion to composition of a commercial conveyor lubricant in alkaline water such that the ratio of hardness to alkalinity is equal to 1.98 to 1 is capable to reduce the failure rate of bottles in the PET compatibility test. COMPARATIVE EXAMPLE F
- An lubricant concentrate composition was prepared by adding 9.0 g of SURFONIC TDA-9 surfactant (available from Huntsman Corporation, Houston TX) to a mixture of 1.3 g of calcium chloride dihydrate, 6.43 g glacial acetic acid, 7.5 g of DUOMEEN OL (available from Akzo Nobel Surface Chemistry LLC, Chicago, IL), 3.Og of DUOMEEN CD (available from Akzo Nobel Surface Chemistry LLC, Chicago, IL), 4.5 g GENAMIN LA302D, and 1.83 g of 45% potassium hydroxide in 63.4 g of softened water.
- SURFONIC TDA-9 surfactant available from Huntsman Corporation, Houston TX
- aqueous lubricant composition was prepared by diluting 5.0 g of the lubricant concentrate solution with 995 g of a solution of 336 ppm sodium bicarbonate in deionized water.
- 5000 ppm of lubricant concentrate in deionized water without added alkalinity was titrated with 0.1 N HCl and the total alkalinity was calculated as described above to be 208 ppm as CaC ⁇ 3.
- the lubricant composition containing 5000 ppm of lubricant concentrate prepared with alkaline water contained 50 ppm calcium chloride (equivalent to 45 ppm hardness as CaCOa), 408 ppm total alkalinity as CaCO 3 , and 336 ppm sodium bicarbonate (equivalent to 200 ppm alkalinity as CaCOs).
- the ratio of hardness as CaCO 3 to total alkalinity as CaC ⁇ 3 was 0.11 to 1
- the ratio of hardness as CaCO 3 to alkalinity as CaC0 3 from the dilution water was 0.23 to 1.
- the lubricant composition was tested for PET compatibility as described above except that twenty ounce "Global Swirl" bottles were substituted for twenty ounce contour bottles whereupon after 28 days of storage under conditions of 100 0 F and 85% relative humidity, 14 of 96 bottles had failed (15%).
- a modified lubricant concentrate composition was prepared by adding 57.9 g of deionized water and 3.05 g of calcium chloride to 39.1 g of the lubricant concentrate of Comparative Example F.
- a lubricant composition was prepared by diluting 12.8 g of the modified lubricant concentrate composition with 987.2 g of a solution of 336 ppm sodium bicarbonate in deionized water.
- 5000 ppm of lubricant concentrate in deionized water without added alkalinity was titrated with 0.1 N HCI and the total alkalinity calculated as described above to be 208 ppm as CaCC ⁇ 3 .
- the resulting aqueous lubricant composition contained 5000 ppm of the lubricant concentrate of Comparative Example F, 440 ppm total calcium chloride (equivalent to 397 ppm hardness as CaCO 3 ), 408 ppm total alkalinity as CaCO 3 , and 332 ppm sodium bicarbonate (equivalent to 200 ppm alkalinity as CaCO 3 ).
- the ratio of hardness as CaCO 3 to total alkalinity as CaCO 3 was 0.97 to 1, and the ratio of hardness as CaCO 3 to alkalinity from the dilution water as CaC ⁇ 3 was 1.98 to 1.
- the amine based lubricant composition was tested for PET compatibility as described above except that the length of the test was 31 days instead of 28, twenty ounce "Global Swirl" bottles were substituted for twenty ounce contour bottles, and on days 4 and 15-17 the relative humidity in the test dropped from 85% to between 10 and 20%, and on days 18 to 31, the relative humidity was 78%. During the PET compatibility test, 0 of 96 bottles had failed (0%). The crazing score for the unfailed bottles in this test was 7.7.
- a solution of deionized water containing 50 ppm alkalinity as CaC ⁇ 3 was prepared by dissolving 0.168 g of sodium bicarbonate in 200Og of deionized water. The ratio of hardness as CaC ⁇ 3 to alkalinity as CaC ⁇ 3 was ⁇ 0.02 to 1.
- the alkaline water solution was tested for PET compatibility as described above. After 28 days of storage under conditions of 100 0 F and 85% relative humidity, 12 of 96 bottles had failed (12 %). The crazing score for the unfailed bottles in this test was 1.7.
- aqueous lubricant composition was prepared which contained 125 ppm Lambent E2140FG silicone emulsion, 7.6 ppm PLURONIC F108 poly(ethylene oxide-propylene oxide) block copolymer, 5.0 ppm methyl paraben, and 19.2% untreated municipal water from Eagan, Minnesota in deionized water.
- the composition contained 50 ppm total alkalinity as CaC ⁇ 3 , 12 ppm calcium, 4 ppm magnesium, total hardness as CaCO 3 equal to 48 ppm, and a ratio of hardness as CaC ⁇ 3 to alkalinity as CaCO 3 equal to 0.95 to 1.
- the lubricant composition was tested for PET compatibility as described above whereupon after 28 days of storage under conditions of 100 0 F and 85% relative humidity, 0 of 96 bottles had failed (0%). The crazing score for the unf ailed bottles in this test was 2.1. What this example shows is that diluting a silicone lubricant with hard alkaline water is capable to reduce the failure rate of bottles in the PET compatibility test relative to soft alkaline water with the same level of alkalinity.
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- Chemical & Material Sciences (AREA)
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- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Containers Having Bodies Formed In One Piece (AREA)
- Non-Alcoholic Beverages (AREA)
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- Filling Of Jars Or Cans And Processes For Cleaning And Sealing Jars (AREA)
Abstract
Description
Claims
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP07845194.5A EP2035534B1 (en) | 2006-06-23 | 2007-05-23 | Aqueous compositions useful in filling and conveying of beverage bottles wherein the compositions comprise hardness ions and have improved compatibility with pet |
EP17203758.2A EP3375853A1 (en) | 2006-06-23 | 2007-05-23 | Aqueous compositions useful in filling and conveying of beverage bottles wherein the compositions comprise hardness ions and have improved compatibility with pet |
ES07845194.5T ES2658542T3 (en) | 2006-06-23 | 2007-05-23 | Aqueous compositions useful in filling and transporting beverage bottles where the compositions comprise hardness ions and have improved compatibility with PET |
JP2009516488A JP5324434B2 (en) | 2006-06-23 | 2007-05-23 | Aqueous compositions useful for filling and transporting polymer bottles and methods for treating and transporting polymer bottles using the aqueous compositions |
AU2007261653A AU2007261653B2 (en) | 2006-06-23 | 2007-05-23 | Aqueous compositions useful in filling and conveying of beverage bottles wherein the compositions comprise hardness ions and have improved compatibility with PET |
CA2654160A CA2654160C (en) | 2006-06-23 | 2007-05-23 | Aqueous compositions useful in filling and conveying of beverage bottles wherein the compositions comprise hardness ions and have compatibility with pet |
KR1020097001526A KR101503720B1 (en) | 2006-06-23 | 2007-05-23 | Aqueous compositions useful in filling and conveying of beverage bottles wherein the compositions comprise hardness ions and have improved compatibility with pet |
MX2008015515A MX2008015515A (en) | 2006-06-23 | 2007-05-23 | Aqueous compositions useful in filling and conveying of beverage bottles wherein the compositions comprise hardness ions and have improved compatibility with pet. |
CN2007800236559A CN101479370B (en) | 2006-06-23 | 2007-05-23 | Aqueous compositions useful in filling and conveying of beverage bottles wherein the compositions comprise hardness ions and have improved compatibility with pet |
BRPI0713037A BRPI0713037B1 (en) | 2006-06-23 | 2007-05-23 | lubricant composition, rinse composition and method for processing and transporting beverage bottles using said compositions |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/426,214 US7741255B2 (en) | 2006-06-23 | 2006-06-23 | Aqueous compositions useful in filling and conveying of beverage bottles wherein the compositions comprise hardness ions and have improved compatibility with pet |
US11/426,214 | 2006-06-23 |
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WO2007149175A2 true WO2007149175A2 (en) | 2007-12-27 |
WO2007149175A3 WO2007149175A3 (en) | 2008-04-03 |
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PCT/US2007/012275 WO2007149175A2 (en) | 2006-06-23 | 2007-05-23 | Aqueous compositions useful in filling and conveying of beverage bottles wherein the compositions comprise hardness ions and have improved compatibility with pet |
Country Status (11)
Country | Link |
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US (3) | US7741255B2 (en) |
EP (2) | EP2035534B1 (en) |
JP (1) | JP5324434B2 (en) |
KR (1) | KR101503720B1 (en) |
CN (1) | CN101479370B (en) |
AU (1) | AU2007261653B2 (en) |
BR (1) | BRPI0713037B1 (en) |
CA (1) | CA2654160C (en) |
ES (1) | ES2658542T3 (en) |
MX (1) | MX2008015515A (en) |
WO (1) | WO2007149175A2 (en) |
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CN107840434B (en) * | 2017-11-10 | 2023-07-28 | 岳京松 | Automatic preparation method and device for soft and hard water in laboratory |
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Also Published As
Publication number | Publication date |
---|---|
BRPI0713037A2 (en) | 2012-04-17 |
JP5324434B2 (en) | 2013-10-23 |
CA2654160A1 (en) | 2007-12-27 |
AU2007261653A1 (en) | 2007-12-27 |
US20100282572A1 (en) | 2010-11-11 |
MX2008015515A (en) | 2009-01-12 |
AU2007261653B2 (en) | 2011-04-07 |
WO2007149175A3 (en) | 2008-04-03 |
EP2035534B1 (en) | 2017-11-29 |
US20120190599A1 (en) | 2012-07-26 |
BRPI0713037B1 (en) | 2017-02-14 |
CN101479370B (en) | 2013-07-24 |
US8097568B2 (en) | 2012-01-17 |
US8703667B2 (en) | 2014-04-22 |
US20070298981A1 (en) | 2007-12-27 |
CA2654160C (en) | 2014-09-23 |
JP2009541173A (en) | 2009-11-26 |
CN101479370A (en) | 2009-07-08 |
EP3375853A1 (en) | 2018-09-19 |
EP2035534A2 (en) | 2009-03-18 |
ES2658542T3 (en) | 2018-03-12 |
KR101503720B1 (en) | 2015-03-19 |
US7741255B2 (en) | 2010-06-22 |
KR20090035686A (en) | 2009-04-10 |
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